CN112962324A - Preparation method of graphene oxide/nano-silver composite coating non-woven material - Google Patents

Preparation method of graphene oxide/nano-silver composite coating non-woven material Download PDF

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CN112962324A
CN112962324A CN202110138355.7A CN202110138355A CN112962324A CN 112962324 A CN112962324 A CN 112962324A CN 202110138355 A CN202110138355 A CN 202110138355A CN 112962324 A CN112962324 A CN 112962324A
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nano
graphene oxide
solution
silver
amino
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CN112962324B (en
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陈宇岳
肖长发
杨竹强
张德锁
陈凯凯
林红
封严
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Handan Hengyong Protective & Clean Products Co ltd
Jiangsu New Vision Advanced Functional Fiber Innovation Center Co ltd
Tianjin Polytechnic University
Suzhou University
Shanghai University of Engineering Science
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Handan Hengyong Protective & Clean Products Co ltd
Jiangsu New Vision Advanced Functional Fiber Innovation Center Co ltd
Tianjin Polytechnic University
Suzhou University
Shanghai University of Engineering Science
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0011Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0086Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0088Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
    • D06N3/009Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin by spraying components on the web
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00Properties of the materials
    • D06N2209/16Properties of the materials having other properties
    • D06N2209/1671Resistance to bacteria, mildew, mould, fungi
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00Specially adapted uses
    • D06N2211/30Filters

Abstract

The preparation method of the graphene oxide/nano-silver composite coating non-woven material comprises the following steps: obtaining an alkaline graphene oxide solution: adjusting the graphene oxide solution to be alkaline by using strong base; obtaining an amino-terminated hyperbranched polymer nano-silver solution: dropwise adding a proper amount of silver nitrate solution into the amino-terminated hyperbranched polymer solution, stirring and reacting; obtaining a graphene oxide/nano silver composite nano material solution: adding the amino-terminated hyperbranched polymer nano-silver solution into the alkaline graphene oxide solution and stirring; obtaining a composite dispersion: centrifuging the graphene oxide/nano-silver composite nano-material solution to obtain a composite material, discarding the supernatant, and adding tetrahydrofuran to disperse into a dispersion liquid; obtaining a composite coated nonwoven material: spraying the dispersion liquid on the surface of the non-woven product, and drying to form the composite coating non-woven material. The scheme is simple and efficient, can rapidly provide high-quality killing protective articles, and has extremely high convenience.

Description

Preparation method of graphene oxide/nano-silver composite coating non-woven material
Technical Field
The invention belongs to the technical field of preparation of functional protective materials, and particularly relates to a preparation method of a graphene oxide/nano-silver composite coating non-woven material.
Background
With the emergence of SARS, avian influenza, new corona and other viruses, protection has become a public health problem which needs to be solved urgently at present, and the requirement on protective materials is higher and higher. The traditional protective textile also has more defects, such as the mask only has the function of blocking viruses in the using process and cannot kill and inhibit the viruses. Therefore, the disposable protective textile effectively blocks the spread of viruses and is a place for gathering the viruses, particularly the protective textile used by infected people. Safety issues with these heavily expended disposable protective textiles during collection and handling are also of paramount importance, and are highly susceptible to worker infections. Therefore, the development of the protective textile with high-efficiency antibacterial and antiviral functions is of great significance.
The graphene and the derivatives thereof are used as new two-dimensional multifunctional nano materials, have the advantages of excellent broad-spectrum antibacterial and antiviral capacity, no induction of bacteria to generate drug resistance, simple preparation process, good biocompatibility and the like, and show good application potential in the fields of biomedicine, home textile, building engineering and the like compared with the traditional antibacterial and antiviral components. The antibacterial and antiviral capacity of the graphene material is mainly based on the mixed synergistic effect of the following mechanisms: physical cutting, membrane surface component extraction, physical capture, oxidative stress (ROS), and the like. Graphene Oxide (GO) is a graphene derivative, oxygen-containing groups such as carboxyl, carbonyl, epoxy and the like are embedded on the surface and the edge of a two-dimensional structure, and the Graphene Oxide (GO) has the characteristics of easiness in dispersion, easiness in surface functionalization and the like.
The silver nano particles show remarkable broad-spectrum antibacterial and antiviral performances due to huge specific surface area and high reaction activity. But the higher surface energy makes the dispersion process extremely unstable and easy to agglomerate, thus influencing the antibacterial and antiviral properties of the product. The graphene oxide with the two-dimensional lamellar structure becomes one of the best substrate materials for the immobilized silver nanoparticles, so that the silver nanoparticles can obtain good dispersibility and stability, and meanwhile, the immobilized silver nanoparticles can effectively inhibit the stacking of graphene lamellar layers, so that the composite nanomaterial with excellent dispersibility is obtained. Therefore, the silver nanoparticles are loaded on the graphene oxide substrate, and under the combined action of the graphene oxide and the silver nanoparticles, the composite antibacterial and antiviral material with better antibacterial and antiviral performances, better broad spectrum and lower drug resistance can be obtained according to the mutual synergistic action of different antibacterial and bactericidal mechanisms of the graphene oxide and the silver nanoparticles.
Fibrous nonwoven protective materials were developed in the 90's of the 20 th century. Firstly, some developed countries in Europe and America utilize advanced non-woven technology to develop a spunlace non-woven fabric which has low cost and appearance and hand feeling close to that of the traditional textile, and the spunlace non-woven fabric can be used as an excellent material for replacing the traditional textile through treatment of 'three-resistance' (anti-alcohol, anti-blood and anti-oil), antistatic, antibacterial and the like and gamma ray disinfection. However, the antistatic pressure of the spunlace nonwoven fabric is relatively low, the virus particle blocking efficiency is also relatively poor, and the spunlace nonwoven fabric can only replace the traditional textile to be used for preparing materials such as common surgical gowns, surgical hole towels and the like, and is not an ideal protective material. Later researchers developed meltblown nonwovens as protective materials, and because the fiber diameter of the meltblown nonwoven is only a few microns, the hydrostatic pressure resistance of the product is greatly improved. Meanwhile, compared with other non-woven materials, the non-woven material adopting the melt-blowing method has higher virus and PM2.5 blocking effects. But as an isolation protection material, the loss of the active inactivation function of the isolation protection material to bacteria and viruses greatly restricts the further improvement of the use safety and the protection effect in the aspect of medical protection materials.
Disclosure of Invention
According to the scheme of the invention, the functional material is produced and prepared in a spraying mode by obtaining the graphene oxide/nano-silver composite material spraying liquid, the method is simple and efficient, can quickly improve high-quality disinfection and sterilization protective articles, and has extremely high convenience.
The preparation method of the graphene oxide/nano-silver composite coating non-woven material comprises the following steps:
obtaining an alkaline graphene oxide solution: adjusting the graphene oxide solution to be alkaline by using strong base;
obtaining an amino-terminated hyperbranched polymer nano-silver solution: dropwise adding a proper amount of silver nitrate solution into the amino-terminated hyperbranched polymer solution, stirring and reacting;
obtaining a graphene oxide/nano silver composite nano material solution: adding the amino-terminated hyperbranched polymer nano-silver solution into the alkaline graphene oxide solution and stirring; the stirring time is preferably 5-24 h;
obtaining a composite dispersion: centrifuging the graphene oxide/nano-silver composite nano-material solution to obtain a composite material, discarding the supernatant, and adding tetrahydrofuran to disperse into a dispersion liquid; the concentration of the dispersion is preferably 1 to 10 g/L;
obtaining a composite coated nonwoven material: spraying the dispersion liquid on the surface of the non-woven product, and drying to form the composite coating non-woven material.
According to the improvement of the preparation method of the graphene oxide/nano-silver composite coating non-woven material, the concentration of graphene oxide in the alkaline graphene oxide solution is 0.1-5 mg/ml.
According to the preparation method of the graphene oxide/nano-silver composite coating non-woven material, disclosed by the invention, the strong base is sodium hydroxide or potassium hydroxide.
According to the preparation method of the graphene oxide/nano-silver composite coating non-woven material, disclosed by the invention, when the amino-terminated hyperbranched polymer nano-silver solution is obtained, the concentration of the amino-terminated hyperbranched polymer in the amino-terminated hyperbranched polymer solution is 0.5-5 g/L.
According to the preparation method of the graphene oxide/nano-silver composite coating non-woven material, provided by the invention, when the amino-terminated hyperbranched polymer nano-silver solution is obtained, the concentration of silver nitrate in the silver nitrate solution is 1-50 mmol/L.
According to the preparation method of the graphene oxide/nano-silver composite coating non-woven material, disclosed by the invention, when the amino-terminated hyperbranched polymer nano-silver solution is obtained, the volume ratio of the amino-terminated hyperbranched polymer solution to the silver nitrate solution is (1-2): 1.
According to the preparation method of the graphene oxide/nano-silver composite coating non-woven material, disclosed by the invention, when the graphene oxide/nano-silver composite nano-material solution is obtained, the volume ratio of the amino-terminated hyperbranched polymer nano-silver solution to the graphene oxide solution is 1 (10-30).
According to the improvement of the preparation method of the graphene oxide/nano-silver composite coating non-woven material, the concentration of the composite material in the dispersion liquid is 0.1-10 g/L.
According to the preparation method of the graphene oxide/nano-silver composite coating non-woven material, disclosed by the invention, a non-woven product is melt-blown non-woven fabric.
In particular, the present application can be produced using the scheme shown below: (1) diluting a graphene oxide aqueous solution to a certain concentration, and adjusting the pH value of the graphene oxide aqueous solution to be alkaline by using a sodium hydroxide solution; (2) dropwise adding a silver nitrate aqueous solution into the amino-terminated hyperbranched polymer aqueous solution, continuously stirring, and heating to boiling for reaction for 3-5 minutes after dropwise adding is finished to obtain an amino-terminated hyperbranched polymer nano-silver solution; (3) adding the amino-terminated hyperbranched polymer nano-silver solution obtained in the step (2) into the alkaline graphene oxide aqueous solution obtained in the step (1) and continuously stirring for a period of time to obtain a graphene oxide/nano-silver composite nano-material aqueous solution; (4) carrying out high-speed centrifugal separation on the graphene oxide/nano-silver composite nano-material aqueous solution, removing supernatant, adding tetrahydrofuran and carrying out ultrasonic dispersion; (5) and (4) spraying the graphene oxide/nano-silver tetrahydrofuran solution obtained in the step (4) onto the surface of the melt-blown non-woven fabric by using a high-pressure spray gun, and drying to obtain the graphene oxide/nano-silver composite coating melt-blown non-woven protective material. Preferably, the injection pressure of the high-pressure spray gun is 0.3-0.6MPa, the injection flow is 1-10ml/s, and the spraying treatment time is 0.5-3 s.
The overall strategy of the scheme is as follows: firstly, preparing aminated nano-silver colloidal solution by utilizing the regulation and control preparation effect of the amino-terminated hyperbranched polymer on nano-silver. And then, carrying out a reaction between amino on the surface of the nano silver and carboxyl in the graphene oxide under an alkaline condition, and covalently grafting the nano silver onto the graphene oxide to form the graphene oxide/nano silver composite nanomaterial. Then, a solution of the composite nanomaterial in which tetrahydrofuran was dispersed was obtained by solvent substitution. And finally, spraying the composite nano material on the surface of the melt-blown non-woven fabric in a high-pressure spraying mode to form the antibacterial and antiviral graphene oxide/nano silver composite nano coating on the surface of the melt-blown fabric.
Compared with the prior art, the method has the following advantages:
the nano silver dispersion liquid with small particle size and high reaction activity can be obtained by regulating and controlling the amino-terminated hyperbranched polymer.
The size of the nano silver particles can be effectively regulated and controlled by adjusting the proportion of the silver ions to the amino-terminated hyperbranched polymer.
The nano silver can be fixed on the graphene oxide sheet layer through the grafting reaction of the amino on the surface of the nano silver and the graphene oxide, so that stable doping modification is formed, the dispersion is uniform, the structure of the composite nano material is stable, the stacking of the graphene oxide sheets can be effectively prevented, and the long-term stable dispersion can be maintained.
The composite graphene oxide sheet can be firmly attached to the surface of the fiber based on the surface energy effect, so that an effective modified coating is formed.
The graphene oxide/nano silver composite nano material has electropositivity, does not influence the electret effect in the melt-blown non-woven fabric, and can improve the filtering performance of the melt-blown fabric.
The melt-blown non-woven fabric after the composite coating has good antibacterial and antiviral effects.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an SEM image of a meltblown nonwoven.
FIG. 2 is an SEM image of spray finished meltblown nonwoven fibers.
Detailed Description
The present invention will be described in detail below with reference to various embodiments. The embodiments are not intended to limit the present invention, and structural, methodological, or functional changes made by those skilled in the art according to the embodiments are included in the scope of the present invention.
Example 1:
adding water into a certain amount of graphene oxide to dilute the graphene oxide to a concentration of 0.5mg/ml, and adjusting the pH value of 55L of diluted graphene oxide aqueous solution to 11 by using sodium hydroxide. Dropwise adding 1L of silver nitrate aqueous solution with the concentration of 0.1mol/L into 1.5L of amino-terminated hyperbranched polymer solution with the concentration of 5g/L, heating to boiling for reaction for 3-5 minutes after dropwise adding, mixing with the graphene oxide solution after pH adjustment, stirring for 10 hours, centrifugally separating to remove supernatant, adding tetrahydrofuran, and performing ultrasonic treatment to obtain dispersion with the concentration of 1 g/L. Spraying the dispersion liquid onto the surface of the melt-blown non-woven fabric by using a high-pressure spray gun, wherein the spraying pressure is 0.45MPa, the spraying flow is 10ml/s, the spraying treatment time is 1.15s, and drying to obtain the graphene oxide/nano-silver composite coating melt-blown non-woven protective material.
Example 2:
adding water into a certain amount of graphene oxide to dilute the graphene oxide to a concentration of 0.1mg/ml, and adjusting the pH value of 137.5L of diluted graphene oxide aqueous solution to 13 by using sodium hydroxide. Dropwise adding 2.75L of silver nitrate aqueous solution with the concentration of 0.05mol/L into 1g/L amino-terminated hyperbranched polymer solution with the concentration of 2.75L, heating to boiling for reaction for 3-5 minutes after dropwise adding, mixing with the graphene oxide solution after pH adjustment, stirring for 24 hours, centrifugally separating to remove supernatant, adding tetrahydrofuran, and performing ultrasonic treatment to obtain dispersion with the concentration of 10 g/L. Spraying the dispersion liquid onto the surface of the melt-blown non-woven fabric by using a high-pressure spray gun, wherein the spraying pressure is 0.56MPa, the spraying flow is 1ml/s, the spraying treatment time is 2.25s, and drying to obtain the graphene oxide/nano-silver composite coating melt-blown non-woven protective material.
Example 3:
adding water to a certain amount of graphene oxide for dilution until the concentration is 5mg/ml, and adjusting the pH value of 75L of diluted graphene oxide aqueous solution to 9 by using sodium hydroxide. Dropwise adding 0.5L of silver nitrate aqueous solution with the concentration of 0.02mol/L into 1L of amino-terminated hyperbranched polymer solution with the concentration of 0.5g/L, heating to boiling for reaction for 3-5 minutes after dropwise adding, mixing with the graphene oxide solution after pH adjustment, stirring for 5 hours, centrifugally separating to remove supernatant, adding tetrahydrofuran, and performing ultrasonic treatment to obtain dispersion with the concentration of 5 g/L. Spraying the dispersion liquid onto the surface of the melt-blown non-woven fabric by using a high-pressure spray gun, wherein the spraying pressure is 0.46MPa, the spraying flow is 6ml/s, the spraying treatment time is 2.5s, and drying to obtain the graphene oxide/nano-silver composite coating melt-blown non-woven protective material.
Example 4:
adding water into a certain amount of graphene oxide to dilute the graphene oxide to a concentration of 1mg/ml, and adjusting the pH value of 90L of diluted graphene oxide aqueous solution to 10 by using sodium hydroxide. Dropwise adding 2L of silver nitrate aqueous solution with the concentration of 0.05mol/L into 2L of amino-terminated hyperbranched polymer solution with the concentration of 4g/L, heating to boiling reaction for 3-5 minutes after dropwise adding, mixing with the graphene oxide solution with the adjusted pH value, stirring for 24 hours, centrifugally separating to remove supernatant, adding tetrahydrofuran, and performing ultrasonic treatment to obtain dispersion with the concentration of 8 g/L. Spraying the dispersion liquid onto the surface of the melt-blown non-woven fabric by using a high-pressure spray gun, wherein the spraying pressure is 0.36MPa, the spraying flow is 8ml/s, the spraying treatment time is 1s, and drying to obtain the graphene oxide/nano-silver composite coating melt-blown non-woven protective material.
Example 5:
adding water into a certain amount of graphene oxide to dilute the graphene oxide to a concentration of 2mg/ml, and adjusting the pH value of 73.2L of diluted graphene oxide aqueous solution to 12 by using sodium hydroxide. Dropwise adding 1.33L of silver nitrate aqueous solution with the concentration of 0.001mol/L into 2.33L of amino-terminated hyperbranched polymer solution with the concentration of 2g/L, heating to boiling for reaction for 3-5 minutes after dropwise adding, mixing with the graphene oxide solution after pH adjustment, stirring for 10 hours, centrifugally separating to remove supernatant, adding tetrahydrofuran, and performing ultrasonic treatment to obtain dispersion with the concentration of 3 g/L. Spraying the dispersion liquid onto the surface of the melt-blown non-woven fabric by using a high-pressure spray gun, wherein the spraying pressure is 0.6MPa, the spraying flow is 4ml/s, the spraying treatment time is 2s, and drying to obtain the graphene oxide/nano-silver composite coating melt-blown non-woven protective material.
Example 6:
a certain amount of graphene oxide is diluted to the concentration of 3mg/ml by adding water, and 94.2L of diluted graphene oxide aqueous solution is taken to adjust the pH value to 10.5 by using sodium hydroxide. And dropwise adding 1.09L of silver nitrate aqueous solution with the concentration of 0.035mol/L into 2.05L of amino-terminated hyperbranched polymer solution with the concentration of 3g/L, heating to boiling for reaction for 3-5 minutes after dropwise adding, mixing with the graphene oxide solution after pH adjustment, stirring for 20 hours, centrifugally separating to remove supernatant, adding tetrahydrofuran, and performing ultrasonic treatment to obtain dispersion liquid with the concentration of 4 g/L. Spraying the dispersion liquid onto the surface of the melt-blown non-woven fabric by using a high-pressure spray gun, wherein the spraying pressure is 0.5MPa, the spraying flow is 2ml/s, the spraying treatment time is 3s, and drying to obtain the graphene oxide/nano-silver composite coating melt-blown non-woven protective material.
Example 7:
adding water to a certain amount of graphene oxide for dilution until the concentration is 4mg/ml, and adjusting the pH value of a diluted graphene oxide aqueous solution to 9.5 by using sodium hydroxide by taking 13.6L. 0.53L of silver nitrate aqueous solution with the concentration of 0.008mol/L is dropwise added into 0.83L of amino-terminated hyperbranched polymer solution with the concentration of 2g/L, after dropwise addition, the mixture is heated to boiling reaction for 3-5 minutes, then the mixture is mixed with the graphene oxide solution after pH adjustment, stirring is carried out for 8 hours, supernatant is separated by centrifugation, tetrahydrofuran is added, and ultrasonic treatment is carried out to obtain dispersion liquid with the concentration of 6 g/L. Spraying the dispersion liquid onto the surface of the melt-blown non-woven fabric by using a high-pressure spray gun, wherein the spraying pressure is 0.4MPa, the spraying flow is 3ml/s, the spraying treatment time is 1.5s, and drying to obtain the graphene oxide/nano-silver composite coating melt-blown non-woven protective material.
Example 8:
adding water into a certain amount of graphene oxide to dilute the graphene oxide to a concentration of 2.7mg/ml, and adjusting the pH value of 50L of diluted graphene oxide aqueous solution to 12.5 by using sodium hydroxide. Adding 1.615L of silver nitrate aqueous solution with the concentration of 0.015mol/L into 2.3L of amino-terminated hyperbranched polymer solution with the concentration of 1.5g/L dropwise, heating to boiling for reaction for 3-5 minutes after dropwise addition, mixing with the alkaline graphene oxide solution after pH adjustment, stirring, centrifugally separating, discarding supernatant, adding tetrahydrofuran, ultrasonically dispersing into dispersion, mixing with the graphene oxide solution after pH adjustment, stirring for 22 hours, centrifugally separating, discarding supernatant, adding tetrahydrofuran, ultrasonically dispersing into dispersion, wherein the concentration of the dispersion is 7 g/L. Spraying the dispersion liquid onto the surface of the melt-blown non-woven fabric by using a high-pressure spray gun, wherein the spraying pressure is 0.3MPa, the spraying flow is 7ml/s, the spraying treatment time is 0.5s, and drying to obtain the graphene oxide/nano-silver composite coating melt-blown non-woven protective material.
The sampling test of example 1 shows that:
FIG. 1 is an SEM image of a meltblown nonwoven. Fig. 2 is an SEM image of fibers in the melt-blown nonwoven fabric after the spray finishing, and it can be seen that the surfaces of the fibers are covered with a dense graphene oxide sheet layer and a large number of nano silver particles are distributed, indicating that the nano silver of the present scheme has a better distribution on the product and a good binding property with the graphene modified structure.
Including but not limited to the samples in the above examples, the stripping rate of the nano silver/graphene is detected to be less than 1% after the samples are subjected to simulated strong sunlight exposure and aging for 5000 hours at 38 ℃. After 10000 times of continuous folding of the sample (one time of folding after completely unfolding and then folding completely and then unfolding) are carried out, the stripping rate of the nano silver/graphene is less than 1 percent. And (3) continuously carrying out turbine water washing on the sample for 75 hours at the water temperature of 60 ℃, and detecting that the stripping rates of the nano silver/graphene are less than 1%.
The samples including but not limited to the samples in the above examples are subjected to antibacterial performance test by the second part absorption method for evaluating the antibacterial performance of GB/T20944.2-2007 textiles, wherein the test strains are staphylococcus aureus (ATCC6538), escherichia coli (ATCC8739) and candida albicans (ATCC10231), and the test results show that the bacteriostatic rate of the samples on the staphylococcus aureus, the escherichia coli and the candida albicans reaches more than 99%.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (9)

1. The preparation method of the graphene oxide/nano-silver composite coating non-woven material comprises the following steps:
obtaining an alkaline graphene oxide solution: adjusting the graphene oxide solution to be alkaline by using strong base;
obtaining an amino-terminated hyperbranched polymer nano-silver solution: dropwise adding a proper amount of silver nitrate solution into the amino-terminated hyperbranched polymer solution, stirring and reacting;
obtaining a graphene oxide/nano silver composite nano material solution: adding the amino-terminated hyperbranched polymer nano-silver solution into the alkaline graphene oxide solution and stirring;
obtaining a composite dispersion: centrifuging the graphene oxide/nano-silver composite nano-material solution to obtain a composite material, discarding the supernatant, and adding tetrahydrofuran to disperse into a dispersion liquid;
obtaining a composite coated nonwoven material: spraying the dispersion liquid on the surface of the non-woven product, and drying to form the composite coating non-woven material.
2. The preparation method of the graphene oxide/nano-silver composite coating non-woven material according to claim 1, wherein the concentration of graphene oxide in the alkaline graphene oxide solution is 0.1-5 mg/ml.
3. The method for preparing a graphene oxide/nano silver composite coating non-woven material according to claim 1, wherein the strong base is sodium hydroxide or potassium hydroxide.
4. The preparation method of the graphene oxide/nano-silver composite coating non-woven material according to claim 1, wherein when the amino-terminated hyperbranched polymer nano-silver solution is obtained, the concentration of the amino-terminated hyperbranched polymer in the amino-terminated hyperbranched polymer solution is 0.5-5 g/L.
5. The preparation method of the graphene oxide/nano-silver composite coating non-woven material according to claim 1, wherein when the amino-terminated hyperbranched polymer nano-silver solution is obtained, the concentration of silver nitrate in the silver nitrate solution is 1-50 mmol/L.
6. The preparation method of the graphene oxide/nano-silver composite coating non-woven material according to claim 4 or 5, wherein when the amino-terminated hyperbranched polymer nano-silver solution is obtained, the volume ratio of the amino-terminated hyperbranched polymer solution to the silver nitrate solution is (1-2): 1.
7. The preparation method of the graphene oxide/nano-silver composite coating non-woven material according to claim 1, wherein when the graphene oxide/nano-silver composite nano-material solution is obtained, the volume ratio of the amino-terminated hyperbranched polymer nano-silver solution to the graphene oxide solution is 1 (10-30).
8. The preparation method of the graphene oxide/nano-silver composite coating non-woven material according to claim 1, wherein the concentration of the composite material in the dispersion is 0.1-10 g/L.
9. The method for preparing a graphene oxide/nano silver composite coating nonwoven material according to claim 1, wherein the nonwoven product is a melt-blown nonwoven fabric.
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